Oil-soluble polyvalent metal salts of acids from oxidized hydrocarbons and process of making same



Patented Dec. 16, 1952 OF ACIDS FROM OXIDIZED HYDROCAR- BONS ANDPROCESS OF MAKING SAME Alfred P. Kozacik and Alexander N. Sachanen, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application January 8, 1948,

Serial No. 1,264

12 Claims. (01.260-1429) The oils in which the polyvalent metal salts of acids derived by the oxidation of hydrocarbons are soluble are primarily oils of vegetable and mineral origin. Oils of particular interest in connection with this invention are vegetable drying oils and the mineral oils ranging from light solvent oils to the heavier, more viscous lubricating oils.

As is well known to those familiar with the art, several processes have been proposed for the preparation of mixtures of organic acids through the oxidation of hydrocarbons, in the presence or absenceof oxidation catalysts, and at atmospheric or superatmospheric pressures. These acids have been converted to the corresponding polyvalent metal salts, which have found limited use as oxidation accelerators for. varnishes, as detergents in lubricating oils, as ingredients of grease, etc. However, when, polyvalent metal salts are prepared from the total acid fraction obtained from oxidation of hydrocarbon mixtures, in accordance with the prior art, the solubilities of these salts in oils, particularly in light petroleum solvents, have been practically negligible. These salts are soluble in highly aromatic solvents, but the use of the latter solvents, is too expensive for practical commercial purposes.

Several processes have been proposed for the preparation of metal salts of acids from oxidized hydrocarbons having greater partial solubility in oils. been lacking and,-as is well known to those familiar with the art, undissolved portions of these salts cannot be tolerated in lubricating oils and in drying oils.

It has now been found that oil-soluble, poly- However, a high degree of solubility has It is more particularly concerned valent metal salts of acids derived from the oxidation of hydrocarbons can'be' prepared by a process which is simple and relatively inexpen sive.

It has now been discovered that acids derived from the oxidation of hydrocarbons can be treated with selective solvents to yield ultimately acids which form polyvalent metal salts of good color and stability, and which have excellent solubility in oils.

Accordingly, it is a broad object of the present invention to provide oil-soluble metal salts of acids derived from the oxidation of hydrocarbons further object is to provide oil-soluble polyvalent metal salts of acids derived from the oxidation of hydrocarbons, having good color and stability. An important object is to provide a process for treating acids derived-by oxidation of hydrocarbons, to obtain polyvalent metal salts having excellent solubility in oils.- Other objects and advantages of the present invention will become apparent to those skilled in the art'from the following description.

Broadly stated, the .present invention provides oil-soluble, polyvalent metal salts of acids derived from the oxidation of hydrocarbons, by a process which comprises oxidizing hydrocarbons,

treating the oxidized product with caustic material to saponify and neutralize the saponifiable and neutralizable matter present in thevoxidized product, separating the saponifiable and neutralizable matter from the thus-treated oxidized product,- treating the saponifiable and neutralizable matter with acidic material, separating the thus-treated saponifiable and neutralizable matter, treating the latter with a light aliphatic hydrocarbon solvent to dissolve oil-soluble organic acidic material, separating the oil-soluble organic acidic material, and converting the same to a polyvalent metal salt.

Any hydrocarbon mixture containing upwards of about by volume of aliphatic and naphthenic hydrocarbons may be oxidized to provide the acids utilized in this invention. In practice, the source of hydrocarbons is a petroleum hydrocarbon fraction boiling'above about 300 F., and preferably, fractions which have a boiling range varying between about 400 F. and about 700 F.

Any method for effecting the oxidation of hydrocarbons may be used to prepare the oxidized hydrocarbons utilized in this invention. ,The procedures disclosed in the patents to Burwell, U. S. Patents Nos. 1,690,768 and 1,690,769, are typical of the operations involved. The source of oxygen may be air, oxygen or inorganic chemicals which readily give up oxygen, such as cerall of the saponifiable constituents present in the products of oxidation, i. e., the esters, lactides, etc., and to neutralize substantially all the organic acids likewise present therein, in accordance with the present invention, the end-products of the oxidation operation are treated with an aqueous solution of caustic material. In practice, an aqueous solution of an alkali-metal hydroxide, such as sodium or potassium hydroxide, is preferred. It must be clearly understood, however, that other alkaline materials may be used, such as, ammonium hydroxide, sodium carbonate, etc. The temperature and time of saponification and neutralization, and the amounts and concentrations of the aqueous solutions of caustic materials may be readily ascertained by any one skilled in the art. Thus, for example, it will be apparent that higher temperatures induce a greater degree of saponification in a shorter period of time. For all practical purposes, the reflux temperature of watergi s preferred.

pr oncooling the product of the saponification and neutralization operation, the mixture will separate into two strata. The heavier, aqueous stratum will comprise water-soluble metalsalts of the organic acids produced during the saponification and neutralization operation. The supernatant stratum will comprise water-insoluble, unsaponifiable and unneutralizable matter.

These strata will be separated from each other by any of the well-knownapplicable techniques, such as decantation, and then, preferably, in order to remove residual amounts .of waterinsoluble, unsaponifiable and u-nneutralizable matter, the aqueous stratum will be washed with solvents which are substantially immiscible with water. Light petroleum ether, diethyl ether, and benzene may be mentioned by way of nonlimiting examples of suitable solvents. The washing operation is preferably carried out at room temperature (20 C.) although higher or lower temperatures may be employed with satisfactory results.

In order to liberate the water-insoluble organic acids from the aqueous stratum containing the water-soluble metal salts of these organic acids, the aqueous stratum is t-reatedwith a mineral acid, dilute or concentrated, such as hydrochloric acid or sulfuric acid, in amounts sufficient to efiect substantially. complete neutralization, a small excess of free acid not being objectionable. As a result of thistreatment, there will be produced an oily layer containing the liberated water-insoluble organicacids. This oily layer of organic acids is first separated from the aqueous stratum, as by decantation, and then is washed with water until free of mineral acid, and dried. Drying may be effected by contacting the wet, oily layer with a suitable drying agent, which does not react chemically with the acids, such as, for example, silica gel, alumina, or anhydrous magnesium sulfate. The oily layer may also be dried by an azeotropic distillation using a suitable solvent.

The separation of the organic acids which produce oil-soluble polyvalent metal salts, from the main body of organic acids present in the oily layer described hereinbefore, is effected by treating the oily layer with an aliphatic hydrocarbon of low molecular weight, such as petroleum ether, pentanes. butanes, etc. During this treatment, the desired organic acids will be dissolved by the solvent, while the undesired organic acids will be precipitated. The amount of aliphatic hydrocarbon solvent to be used will ordinarily 4 vary between about 3 and about 10 volumes per one volume of oily layer.

Separation of the phases is efiected by filtration and/or by decantation. The solvent present in the solution containing the desired organic acids is subsequently removed by distillation, thereby yielding the desired organic acids in more or less pure form for the preparation ultimately of the oil-soluble salts. This treatment is carried out ordinarily at room temperature (20 C.) although, if desired, higher or lower temperatures may be used.

Oil-soluble polyvalent metal salts of the organic acids thus isolated are prepared by any of the usual methods for preparing salts of organic acids, such as, for example, double decomposition reactions, replacement of acidic hydrogen with a metal, or a dehydration reaction of the organic acid with a metal oxide. In a double decomposition reaction, for example, the organic acids may be converted into the alkali metal salts by treatment with an aqueous solution of alkali metal hydroxide and these salts are then dissolved in water. The resultant aqueous solution ,is treated with an aqueous solution of a watersoluble salt of the desired polyvalent metal, thereby precipitating the desired oil-soluble, water-insoluble polyvalent metal salts. These salts may be isolated by dissolving them in a light hydrocarbon solvent, such as light petroleum ether or benzene, and separating the layers thus produce-d. The solvent may be removed by evaporation or distillation, and the desired oilsoluble, polyvalent metal salts thus obtained in pure form. Water-soluble salts of the polyvalent metals utilizable herein include the watersoluble halides, nitrates, acetates, etc. Nonlimiting examples of these salts are chlorides or acetates of cobalt, lead, manganese, copper, etc.

Although the double decomposition method, described hereinbefore, is the preferred method for preparing polyvalent metal salts of the organic acids, other methods of salt formation may be used to prepare polyvalent metal salts of organic acids in accordance with the present invention. For example, a solution of the organic acids in an appropriate solvent, such as methyl alcohol, is refluxed with a quantity of zinc dust, slightly in excess of the amount of zinc equivalent to the acidity of the acids, thereby replacing acidic hydrogen of the acids and forming the zinc salts thereof. The resulting solution of zinc salts is clarified by filtration. The solvent is removed by distillation and the desired oil-soluble zinc salts are thus obtained. By this procedure, metal salts may be prepared from any finely-divided metal, such as iron, aluminum, tin, and calcium, which will replace acidic hydrogen. By still another procedure, the organic acids are heated with a metallic oxide, such as zinc oxide, calcium oxide, etc., at about 0., or higher, to drive 01f the water formed in the reaction involved, thereby yielding the desired oil-soluble, polyvalent metal salts. If desired, this procedure may be carried out in an appropriate solvent.

. soluble polyvalent metal salts in accordance with this invention.

Example 1 Light white oil (acid-treated kerosene) having a boiling range varying between about 462 F. and about 520 F., and a specific gravity of 0.8072, was oxidized under atmospheric pressure, at 302 F. Oxidation was effected by charging oxygen at the rate of 885 cubic centimeters per minute for about 30 hours. The resulting product had a neutralization number (number of milligrams of KOH equivalent to one gram of substance) of 118.4 and a saponification number of 282.

The resulting oxidized light white oil was saponified and neutralized with an aqueous solution of sodium hydroxide at reflux temperature (212 F.) for about four hours. 'After standing and cooling, the reaction mixture formed two layers, namely, a supernatent layer of unsaponifiable and unneutralizable matter and an alkaline aqueous solution of the sodium salt of the saponifiable and neutralizable matter. The layer of saponifiable and neutralizable matter was separated and then washed with benzene to remove residual'unsaponifiable and unneutralizable matter. The alkaline layer was acidified with an amount of concentrated hydrochloric acid equivalent to the sodium hydroxide used for saponification. The layer of water-insoluble organic acids was separated and washed free of watersoluble organic acids with distilled water. The washed water-insoluble organic acids were dried by adding benzene and distilling oif the binary mixture of benzene and water. The resulting water-insoluble acids had the following properties:

A solvent extraction of these organic acids was carried out as follows: Three hundred grams of these organic acids were placed in a 3-liter Erlenmeyer flask. Light petroleum ether was then added gradually. After about 500 cubic centimeters of petroleum ether had been added, a precipitation of dark semi-solid material commenced. An additional 1500 cubic centimeters of petroleum ether were added and then the solution was filtered by suction through a layer of filtering clay to remove a peppery dispersion. Another 500 cubic centimeters of petroleum ether were then added to the filtrate and the mixture was allowed to stand for hours, at the end of which time a small substratum separated.

The petroleum ether was distilled from the mixture at atmospheric pressure; final traces being removed under vacuum. The product was a clear, dark amber-red fiuid weighing 171.5

grams (57.3 per cent yield, based on the total 6 acids which were solvent treated) and had, the following properties:

Neutralization number 211.7 Specific gravity 60/60 F 0.9779 Color (Lovibond) Polyvalent metal salts were prepared from the acids thus obtained in the following manner:

Example II A sample of the petroleum ether-soluble acids, obtained in Example I, was completely neutralized with a dilute sodium hydroxide aqueous solution. An aqueous solution of cobaltous chloride was added thereto until the formation of the cobaltous salts of the acids was complete as indicated by the absence of any additional precipitation with excess cobaltous chloride. The resultant mixed cobaltous salts were separated from the aqueous phase, washed, and dried. This salt contained 8.58 per cent cobalt. It was completely soluble in benzene and in a commercial low-aromatic solvent (containing about 15% aromatics).

Example III Example IV By the same procedure used in Example II, the mixed manganous salts of the acids obtained in Example I were prepared using an aqueous solution of manganous chloride in place of the cobaltous chloride solution. This salt contained 9.88 per cent manganese. It had sufficient solubility to form a solution in a commercial low-aromatic solvent containing 81.3 per cent of the salt, by weight. I a 7 Example V By the same procedure used in Example 11, the mixed copper salts of the acids obtained in Example I were prepared using an aqueous solution of cupric sulfate in place of the cobaltous chloride solution. This salt contained 8.9 per cent copper. It was soluble in benzene and-in a commercial low-aromatic solvent.

It will be apparent that the present invention discloses a simple and inexpensive process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from oxidized hydrocarbons. These salts have good color and stability, and they are readily soluble in oils. These salts find wide application in diverse fields, as will be obvious to those skilled in the art. For example, the transitional metal salts of these acids (considered to be oxidation accelerators) are useful as additives in paints and varnishes having oil bases, for the purpose of accelerating the drying thereof. The solubility of the salts in oils insures a finish which is unmarred by the presence of insoluble particles. Various polyvalent metal salts of these acids may be added to petroleum oils of all types, particularly, lubricating oils, to improve the properties thereof, especially in those cases Where a single, homogeneous solution is desired.

Although the present invention has been described in conjunction with preferred embodiments, it is to. be understood that modificationsand variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

What is claimed is:

l. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of a caustic material to saponiiy and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the caustic treated product, acidifying said saponified and neutralized matter with acidic material to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with an aliphatic hydrocarbon solvent to dissolve oil-soluble organic acidic material therefrom, isolating said oilsoluble organic acidic material, and converting the same to a polyvalent metal salt.

2. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating th oxidized product with an aqueous solution of an alkalimetal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide, acidifying said saponified and neutralized matter with mineral acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with an aliphatic hydrocarbon solvent to dissolve oilsoluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a polyvalent metal salt.

3. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and wa- 8 ter-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acid material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a copper salt.

4. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkalimetal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a cobalt salt.

5. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about 80 by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkalimetal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and waterinsoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a manganese salt.

6. Oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons obtained by a process which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutra- 7. A process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from the oxidization of hydrocarbons, which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of a caustic material to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the caustic treated product, acidifying said saponified and neutralized matter with acidic material to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with an aliphatic hydrocarbon solvent to dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a polyvalent metal salt.

8. A process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons, which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide, acidifying said saponified and neutralized matter with mineral acid to produce a mixture containing watersoluble and water-insoluble acidic saponfiable and neutralizable matter, isolating the waterinsoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with an aliphatic hydrocarbon solvent to dissolve oilsoluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a polyvalent metal salt.

9. A process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons, which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutral l0 ized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to' dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a copper salt. 10. A process for the preparation of oil-soluble polyvalent metal salts of .organic acids derived from the oxidation of hydrocarbons, which comprises oxidizin a hydrocarbon mixture containing upwards of about by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutral ized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the Water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic maiterial, and converting the same to a cobalt sa 11. A process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons, which comprises oxidizing a hydrocarbon mixture containing upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product, treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the water-insoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acidic material therefrom, isolating said oil-soluble organic acidic material, and converting the same to a manganese salt.

12. A process for the preparation of oil-soluble polyvalent metal salts of organic acids derived from the oxidation of hydrocarbons, which comprises oxidizing a hydrocarbon mixture containmg upwards of about 80% by volume of aliphatic and naphthenic hydrocarbons and boiling above about 300 F. to produce an oxidized product,

11 treating the oxidized product with an aqueous solution of an alkali-metal hydroxide to saponify and neutralize the saponifiable and neutralizable matter present in said oxidized product, separating the saponified and neutralized saponifiable and neutralizable matter from the unsaponifiable and unneutralizable matter in the alkali-metal hydroxide treated product, acidifying said saponified and neutralized matter with hydrochloric acid to produce a mixture containing water-soluble and water-insoluble acidic saponifiable and neutralizable matter, isolating the water-insoluble acidic saponifiable and neutralizable matter therefrom, treating the waterinsoluble acidic saponifiable and neutralizable matter with light petroleum ether to dissolve oil-soluble organic acidic material therefrom, iso- I2 lating said oil-soluble organic acidic material, and converting the same to a lead salt.

ALFRED P. KOZACIK. ALEXANDER N. SACHANEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. OIL-SOLUBLE POLYVALENT METAL SALTS OF ORGANIC ACIDS DERIVED FROM THE OXIDATION OF HYDROCARBONS OBTAINED BY A PROCESS WHICH COMPRISES OXIDIZING A HYDROCARBON MIXTURE CONTAINING UPWARDS OF ABOUT 80% BY VOLUME OF ALIPHATIC AND NAPHTHENIC HYDROCARBONS AND BOILING ABOVE ABOUT 300* F. TO PRODUCE AN OXIDIZED PRODUCT, TREATING THE OXIDIZED PRODUCT WITH AN AQUEOUS SOLUTION OF A CAUSTIC MATERIAL TO SAPONIFY AND NEUTRALIZE THE SAPONIFIABLE AND NEUTRALIZABLE MATTER PRESENT IN SAID OXIDIZED PRODUCT, SEPARATING THE SAPONIFIED AND NEUTRALIZED SAPONIFIED AND NEUTRALIZABLE MATTER FROM THE UNSAPONIFIABLE AND UNNEUTRALIZABLE MATTER IN THE CAUSTIC TREATED PRODUCT, ACIDIFYING SAID SAPONIFIED AND NEUTRALIZED MATTER WITH ACIDIC MATERIAL TO PRODUCE A MIXTURE CONTAINING WATER-SOLUBLE AND WATER-INSOLUBLE ACIDIC SAPONIFIABLE AND NEUTRALIZABLE MATTER, ISOLATING THE WATER-INSOLUBLE ACIDIC SAPONIFIABLE AND NEUTRALIZABLE MATTER THEREFROM, TREATING THE WATER-INSOLUBLE ACIDIC SAPONIFIABLE AND NEUTRALIZABLE MATTER WITH AN ALIPHATIC HYDROCARBON SOLVENT TO DISSOLVE OIL-SOLUBLE ORGANIC ACIDIC MATERIAL THEREFROM, ISOLATING SAID OILSOLUBLE ORGANIC ACIDIC MATERIAL, AND CONVERTING THE SAME TO A POLYVALENT METAL SALT. 